KR101661771B1 - Impact-modified polycarbonate compositions having high hydrolysis resistance and a light natural colour - Google Patents

Abstract

A) an aromatic polycarbonate and / or an aromatic polyester carbonate; B) a graft polymer obtainable by co-precipitation of a mixture of two or more graft polymer dispersions B.1 and B.2, wherein the graft polymer component B.1 is obtained by using at least one redox system as initiator Characterized in that the graft polymer component B.2 is prepared using at least one persulfate compound as an initiator); C) optionally, vinyl (co) polymer and / or polyalkylene terephthalate; D) optionally, a phosphorus containing flame retardant; E) one or more phenolic antioxidants; F) optionally, neutral phosphorus containing or sulfur containing auxiliary stabilizers (synergists); And G) optionally, an additive, wherein the polycarbonate composition is characterized by excellent hydrolytic resistance and light natural color in an optimal state, and a use for the production of a molded article of the polycarbonate composition, .

Description

[0001] IMPACT-MODIFIED POLYCARBONATE COMPOSITIONS HAVING HIGH HYDROLYSIS RESISTANCE AND LIGHT NATURAL COLOR [0002] This invention relates to impact-modified polycarbonate compositions having excellent hydrolytic resistance and light natural color,

The present invention relates to a thermoplastic polycarbonate composition (molding composition) impact modified with a specially prepared and treated graft polymer, a process for its production and a molded article produced therefrom.

Thermoplastic molding compositions including polycarbonate and ABS polymers have long been known. For example, DE-A 1 170 141 discloses an easy-to-process molding composition comprising a graft polymer of a monomer mixture of an aromatic vinyl hydrocarbon and acrylonitrile on polycarbonate and polybutadiene.

DE-A 1 810 993 emphasizes the improved heat resistance of ABS graft polymers or mixtures of polycarbonates with alpha -methylstyrene as the main component.

The gist of DE-A 22 59 565 and DE-A 23 29 548 is the improved flow-line strength of the PC / ABS molding composition wherein a graft polymer having a specific particle size is used as a component of the ABS component. EP-A 0 704 488 discloses a thermoplastic molding composition having a particle diameter of 0.20 to 0.35 μm.

DE-A 28 18 679 teaches that the PC / ABS blend exhibits a particularly high low temperature strength when the ABS polymer contains two graft copolymers with different graft degrees.

Also, depending on the purity and additive content of the impact modifier, such as ABS (acrylonitrile-butadiene-styrene terpolymer), the polycarbonate composition containing the graft polymer as an impact modifier has different stability against hydrolysis and heat load . Thus, BS Patty , L. Novak and H. Phan , "Thermal and hydrolytic stability of polycarbonate / acrylonitrile-butadiene-styrene based blends", Society of Automotive Engineers, Special Publication SP (2005), SP-1960 (Advances in Plastic Components, Processes and Technologies) 145-151 discloses polycarbonate compositions that exhibit remarkably superior hydrolytic stability and thermal stability compared to the case of using emulsified ABS as a modifier using bulk ABS as a modifier. Here, different aspects of the polycarbonate / bulk ABS composition as compared to the polycarbonate / emulsified ABS composition are that the manufacturing process for emulsified ABS compared to bulk ABS can be used as an adjunct to a number of different chemicals such as emulsifiers, , Stabilizers, salts, and the like, and such chemicals also include those that can cause decomposition of the polycarbonate. Another advantage of the polycarbonate / block ABS composition is particularly light natural color (natural color), which has a particularly favorable effect on the coloration of the molded article comprising said composition.

Some polycarbonate compositions containing an emulsifying graft polymer as an impact modifier have some technical advantages in terms of, for example, surface finish (gloss) compared to polycarbonate compositions containing bulk ABS, so that in some applications, It is advantageous to use a polymer. When a high hydrolytic stability is required, it is preferable that the emulsion graft polymer to be used is used in a large amount in terms of, for example, the purity of the graft polymer, the process of its production and the absence of a specific auxiliary substance in its production Requirements must be given.

For example, EP-A 0 900 827 discloses a thermostable impact-modified polycarbonate composition containing an emulsified graft polymer, and this composition has few components that decompose the polycarbonate. In order to obtain an emulsified graft polymer having almost no components for decomposing polycarbonate, it is necessary to completely remove the above components at every stage of the emulsification process or to remove the graft emulsion from the emulsified graft polymer prepared, for example, After the condensation of the components, the components must be completely removed by washing. In particular, the use of carboxylate containing auxiliary substances (such as emulsifiers, buffer solutions, etc.) should be avoided because these auxiliary materials degrade the polycarbonate. The polycarbonate compositions known from EP-A 0 900 827 contain emulsifying graft polymers of the MBS and ABS type, prepared using sulfate-containing and / or sulfonate-containing emulsifiers. The emulsifier often causes undesirable discoloration of the molding composition.

Through WO-A 99/01489, emulsified graft polymers of the ABS type are known, which are prepared using various emulsifiers. Specifically, a conventional carboxylate-containing emulsifier is mentioned as an emulsifier usable in the production of the polymer. The patent specification also teaches in particular how to prepare light colored ABS molding compositions in which the processing and the acrylonitrile content in the graft polymer and matrix components (SAN resin) play a particularly important role do. Through WO-A 99/01489 it can be seen that, among other things, compositions containing emulsifying ABS have a specific tendency towards yellowing or even browning. Such yellowing or browning is distinguished by a yellowness index which is well over 30 and far above 50. The yellowness index can be determined by several factors, for example, the rubber and acrylonitrile content of ABS, the additives during the emulsion polymerization and the treatment, and optionally, the purification of the graft polymer and the processing conditions of the molding composition, Lt; / RTI > The yellowing or brown decoloring is frequent at high temperatures, for example, occurring during processing by injection molding or mixing with additives during compounding in an extruder.

WO-A 2004/050765 discloses a method for producing an impact which combines excellent surface properties (especially very few defects, so-called "fish eyes"), good flow behavior and excellent stress cracking resistance Teaches the preparation of modified compositions. To achieve this goal, co-precipitated graft polymers prepared by emulsion polymerization processes are used, wherein one or more graft polymers prepared by redox initiation are reacted in the latex stage (i.e., as a polymer dispersion ) Inorganic peroxide initiator and then co-precipitated and melt blended with a thermoplastic resin or a mixture of thermoplastic resins, including polycarbonate, polyester carbonate, polyamide and polyoxymethylene. According to WO-A 2004/050765, the composition thus prepared, in particular a composition containing polycarbonate, polyester carbonate and polyester, has been found to be excellent in improving the hydrolytic stability and improving the inherent color (natural color) There is no bar.

An object of the present invention is to provide an impact modified polycarbonate composition which is distinguished in that it has excellent hydrolytic resistance and light natural color in an optimal state. Specifically, the object of the present invention is to provide an impact modified poly (arylene ether) copolymer which is distinguished in that it maintains excellent flame retardancy (V-0 evaluation for a wall thickness of 1.5 mm) Carbonate composition of the present invention.

It has unexpectedly been found that the object of the present invention described above is achieved by a composition or a molding composition comprising the following A) to G):

A) an aromatic polycarbonate and / or an aromatic polyester carbonate;

B) a graft polymer obtainable by co-precipitation of a mixture of two or more graft polymer dispersions, wherein the graft polymer component B.1 is prepared using at least one redox system as an initiator and the graft polymer component B.2 is characterized by being prepared using at least one persulfate compound as an initiator);

C) optionally, vinyl (co) polymer and / or polyalkylene terephthalate;

D) optionally, a phosphorus containing flame retardant;

E) one or more phenolic antioxidants;

F) optionally, neutral phosphorus containing or sulfur containing auxiliary stabilizers (synergists); And

G) Optionally, additive.

A) to G) are preferred:

A) 10 to 99 parts by weight, preferably 40 to 95 parts by weight, particularly preferably 50 to 85 parts by weight of an aromatic polycarbonate and / or an aromatic polyester carbonate;

B) a graft polymer obtainable by co-precipitation of a mixture of two or more graft polymer dispersions B.1 and B.2, wherein the graft polymer component B.1 is obtained by using at least one redox system as initiator 1 to 50 parts by weight, preferably 4 to 30 parts by weight, particularly preferably 12 to 30 parts by weight, of the graft polymer component B.2 is characterized in that it is prepared by using at least one persulfate compound as an initiator) 25 parts by weight;

C) 0 to 40 parts by weight, preferably 1 to 30 parts by weight, particularly preferably 3 to 25 parts by weight of a vinyl (co) polymer and / or a polyalkylene terephthalate;

D) 0 to 50 parts by weight, preferably 2 to 30 parts by weight, particularly preferably 10 to 20 parts by weight, of the phosphorus-containing flame retardant, based on the sum of the weight of the component A + B + C in each case;

E), 0.005 to 1 part by weight, preferably 0.01 to 0.5 part by weight, particularly preferably 0.02 to 0.3 part by weight of at least one phenolic antioxidant based on the sum of parts by weight of component A + B + C, Weight part;

F) 0 to 4 parts by weight, preferably 0.01 to 4 parts by weight, of a neutral phosphorus-containing or sulfur-containing auxiliary stabilizer (hereinafter also referred to as ascending agent) based on the sum of the weight of the component A + B + 2 parts by weight, particularly preferably 0.05 to 0.5 parts by weight; And

G) 0 to 50 parts by weight, preferably 0.5 to 25 parts by weight of an additive, based on the sum of the components A + B + C in each case.

   All data for the parts by weight herein are normalized so that the sum of the parts by weight of all the components A + B + C in the composition is equal to 100 in total.

The above components and other components that can be used in the composition according to the present invention are illustrated below.

Component A

Aromatic polycarbonates and / or aromatic polyester carbonates by Component A suitable for the present invention are either known from the literature or can be prepared by methods known from the literature (in the case of aromatic polycarbonate production, DE-A 2 72 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 2 714 546, 3 000 610, DE-A 3 832 396; for the preparation of aromatic polyester carbonates, see for example DE-A 3 077 934).

The preparation of aromatic polycarbonates can be carried out, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, Monophenol) is arbitrarily used and an interface polycondensation method using a trifunctional or trifunctional or higher branching agent (for example, triphenol or tetraphenol) is optionally used. The aromatic polycarbonate may be produced by a melt polymerization method by reacting diphenol with, for example, diphenyl carbonate.

The diphenols used to prepare the aromatic polycarbonate and / or the aromatic polyester carbonate are preferably represented by the following formula (I)

(I)

In this formula,

A is a single bond, C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ Cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₂ -, C ₆ -C _{12, in} which other aromatic rings optionally containing heteroatoms may be condensed, Arylene, or a group represented by the following formula (II) or (III): < EMI ID =

≪ RTI ID = 0.0 &

(III)

;

;

B is in each case C ₁ -C ₁₂ alkyl, preferably methyl, halogen, preferably chlorine and / or bromine;

x is, independently at each occurrence, 0, 1 or 2;

p is 1 or 0;

R ⁵ and R ⁶ may be individually selected for each X ¹ and are independently of each other hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen, methyl or ethyl;

X ¹ is carbon;

m is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X ^1, R ⁵ and R ⁶ are simultaneously alkyl.

Preferred diphenols are selected from the group consisting of hydroquinone, resorcinol, dihydroxydiphenol, bis (hydroxyphenyl) -C ₁ -C ₅ -alkane, bis (hydroxyphenyl) -C ₅ -C ₆ -cycloalkane, bis Bis (hydroxyphenyl) ether, bis (hydroxyphenyl) sulfoxide, bis (hydroxyphenyl) ketone, bis (hydroxyphenyl) sulfone and a, Brominated and / or ring chlorinated derivatives.

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) Hexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, and These brominated and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro- 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable.

Diphenol can be used alone or as a mixture. Diphenol is known from the literature or can be obtained by methods known from the literature.

Examples of suitable chain terminations for preparing thermoplastic aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, as well as long chain alkylphenols such as 4- [2 - (2,4,4-trimethylpentyl)] phenol, 4- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or a monoalkyl having a total of 8 to 20 carbon atoms in an alkyl- Phenol or dialkylphenol such as 3,5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) - (3,5-dimethylheptyl) phenol. The amount of chain terminator used is generally from 0.5 mol% to 10 mol%, based on the total number of moles of diphenols used in each case.

The weight average molecular weight of the thermoplastic aromatic polycarbonate intermediate value (M _w, GPC, measured by ultracentrifugation or scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably 24,000 To 32,000 g / mol.

The thermoplastic aromatic polycarbonate is preferably contained in a known manner, preferably by incorporating 0.05 to 2.0 mol% of a compound having three or more functional groups, such as three or more phenolic groups, based on the sum of the diphenols used, Can be formed.

Both homopolycarbonate and copolycarbonate are suitable. In the present invention, in order to prepare the copolycarbonate by the component A, it is preferred to use a mixture of 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols used, Polydiorganosiloxanes may also be used. Such polydiorganosiloxanes are known (US Pat. No. 3,149,644) and can be prepared by methods known from the literature. A process for the preparation of copolycarbonates containing polydiorganosiloxanes is disclosed in DE-A 3 334 782.

Preferred polycarbonates include, besides bisphenol A homopolycarbonate, up to 15 mole%, based on the total moles of diphenol, of other diphenols, particularly 2,2-bis (3,5-dibromo 4-hydroxyphenyl) propane and bisphenol A. < / RTI >

The aromatic dicarboxylic acid dihalide used for producing the aromatic polyester carbonate is a diacid dichloride of isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid and 2,6-naphthalene dicarboxylic acid desirable.

Particularly preferred are diacid dichloride mixtures of isophthalic acid and terephthalic acid in a ratio of 1:20 to 20: 1. In producing the polyester carbonate, a carbonate halide, preferably phosgene, is also used as the bifunctional acid derivative.

Chain terminations suitable for preparing aromatic polyester carbonates are, in addition to the aforementioned monophenols, the chlorocarbonic esters of these and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C ₁ -C ₂₂ alkyl groups or halogen atoms And C ₂ -C ₂₂ monocarboxylic acid chloride.

The amount of the chain terminator is 0.1 to 1 mole based on the molar amount of diphenol in the case of the phenolic chain terminator and in the case of the monocarboxylic acid chloride chain terminator in terms of the number of moles of the dicarboxylic acid dichloride, To 10 mol%.

In addition, the aromatic polyester carbonate may also contain an incorporated aromatic hydroxycarboxylic acid.

The aromatic polyestercarbonates can be branched and branched in a linear and known manner (see DE-A 2 940 024 and DE-A 3 007 934).

As the branching agent, for example, a trifunctional or multifunctional acyl chloride such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-, 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1 , 4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride in an amount of 0.01 to 1.0 mol% (based on the used dicarboxylic acid dichloride), or using a trifunctional or multifunctional phenol, (4-hydroxyphenyl) hept-2-ene, 4,6-dimethyl-2,4,6-tri- (4- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, tetra- Methane, 2,6-bis (2-hydroxy- 2- (2,4-dihydroxyphenyl) propane, tetra- (4- [4-hydroxyphenylisopropyl] phenoxy) Methane, 1,4-bis [4,4'-dihydroxytriphenyl) methyl] benzene can be used in an amount of 0.01 to 1.0 mol% based on the used diphenol. The phenolic branching agent may be initially supplied with the diphenol, and the acid chloride branching agent may be added with the acid dichloride.

In the thermoplastic aromatic polyester carbonate, the fraction of the carbonate structural unit can be arbitrarily changed. The proportion of the carbonate group is preferably up to 100 mol%, particularly preferably up to 80 mol%, more preferably up to 50 mol%, based on the sum of the ester group and the carbonate group. The ester and carbonate moieties of the aromatic polyestercarbonate may be present in block form within the polycondensate or may be randomly distributed.

The relative solution viscosity (? _Rel ) of the aromatic polycarbonate and the polyester carbonate is in the range of 1.18 to 1.4, preferably in the range of 1.20 to 1.32 (in a solution of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 占 폚 .

The thermoplastic aromatic polycarbonate and polyester carbonate may be used alone or in any mixture.

Component B

Component B is a graft polymer obtainable by co-precipitation of a mixture of two or more graft polymer dispersions B.1 and B.2, wherein B.1 and B.2 each comprise at least one of the following main chains (ii ) Of at least one vinyl monomer (i)

i) from 15 to 60% by weight, preferably from 25 to 60% by weight, particularly preferably from 30 to 50% by weight, of one or more vinyl monomers;

ii) from 85 to 40% by weight, preferably from 75 to 40% by weight of one or more main chains having a glass transition temperature lower than 10 ° C, preferably lower than 0 ° C, particularly preferably lower than -20 ° C, Is 70 to 50% by weight.

The main chain of the graft polymer obtainable by the co-precipitation generally has an average particle size (d ₅₀ value) of 0.05 to 5 μm, preferably 0.1 to 0.5 μm, particularly preferably 0.2 to 0.4 μm.

Monomer i) is preferably a mixture of i1) and i2)

i1) a vinyl aromatic and / or ring-substituted vinyl aromatics (e.g., styrene, α- methyl styrene, p- methyl styrene, p- chlorostyrene) and / or (meth) acrylic acid (C ₁ -C ₈₎ alkyl esters (For example, methyl methacrylate, ethyl methacrylate) 50 to 99 parts by weight, and

i2) a vinyl cyanide (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈₎ alkyl esters (e.g. methyl methacrylate, n- butyl acrylate, t- Butyl acrylate) and / or derivatives of unsaturated carboxylic acids (e.g., anhydrides and imides such as maleic anhydride and N-phenylmaleimide).

Preferred monomers i1) are selected from at least one monomeric styrene, a-methylstyrene and methyl methacrylate, and the preferred monomers i2) are selected from at least one monomeric acrylonitrile, maleic anhydride and methyl methacrylate.

Particularly preferred monomers are i1) styrene and i2) acrylonitrile.

Suitable backbone chains ii) for graft polymers B.1 and B.2 are, for example, diene rubbers, EP (D) M rubbers, i.e. rubbers based on ethylene / propylene and optionally diene monomers and acrylates, polyurethanes, , Chloroprene, and ethylene / vinyl acetate rubbers.

The preferred main chain ii) is a diene rubber. In the present invention, the term dienom rubber means a copolymerizable monomer (e.g., i1) and i2) other than a mixture of a diene rubber (e.g., a rubber mainly composed of butadiene, isoprene and the like) or a diene rubber, Styrene copolymer containing up to 30% by weight of styrene, provided that the glass transition temperature of component ii) is less than 10 ° C, preferably less than 0 ° C , Particularly preferably less than -20 占 폚.

Pure polybutadiene rubber is particularly preferred.

Suitable acrylate rubbers according to ii) of polymers B.1 and B.2 are preferably polymers of alkyl acrylates optionally containing up to 40% by weight of other polymerizable ethylenically unsaturated monomers based on ii). Preferred polymerizable acrylates include C ₁ -C ₈ alkyl esters such as the methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C ₁ -C ₈ -alkyl esters such as chloroethyl acrylate, and mixtures of such monomers.

For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of the crosslinking monomer include an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and an unsaturated monohydric alcohol having 3 to 12 carbon atoms or an ester of 2 to 4 OH groups and a saturated polyol having 2 to 20 carbon atoms, Such as ethylene glycol dimethacrylate, allyl methacrylate; Polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; Polyfunctional vinyl compounds such as divinylbenzene and trivinylbenzene; And triallyl phosphate and diallyl phosphate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomer triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzene. The amount of crosslinking monomer is 0.02 to 5% by weight, especially 0.05 to 2% by weight, based on the main chain ii).

When cyclic crosslinking monomers having three or more ethylenically unsaturated groups are used, it is advantageous to limit the amount thereof to less than 1% by weight of the main chain ii).

Examples of preferred "other" polymerizable ethylenically unsaturated monomers which may optionally be used in addition to the acrylate for preparing the backbone chain ii) include acrylonitrile, styrene,? -Methylstyrene, acrylamide, vinyl-C ₁ -C ₆ Alkyl ethers, methyl methacrylate, and butadiene. The acrylate rubber preferred as the main chain ii) is an emulsion polymer having a gel content of 60% by weight or more.

Other suitable backbones according to ii) are those having graft active sites as disclosed in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539 It is a silicone rubber.

The gel content of the main chain ii) is measured at 25 ° C in a suitable solvent (eg toluene) (M. Hoffmann, H. Kromer R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).

The weight average particle size median d ₅₀ is the value above and below which 50 wt% of the particles are present. This value can be measured by ultracentrifugation measurement (W. Scholtan, H. Lange, Kolloid-Z. And Z. Polymere 250 (1972), 782-796).

Particularly preferred polymers B.1 and B.2 are described, for example, in DE-A 2 035 390 (= US-A 3 644 574) or DE-A 2 248 242 (= GB-PS 1 409 275) Ullmann, Enzyklopadie der Technischen Chemie, vol. 19 (1980), pp. 280 ff) (preferably made by emulsion polymerization). The gel content of the main chain ii) is generally at least 30% by weight, preferably at least 40% by weight (measured in toluene).

Graft polymers having a core-shell structure are preferred.

The graft copolymers B.1 and B.2 are generally prepared by free radical polymerization, preferably by emulsion polymerization.

The graft polymers B.1 used according to the invention are prepared via redox initiation.

Redox initiator systems suitable for the present invention generally consist of an organic oxidizing agent and a reducing agent, optionally with further heavy metal ions in the reaction medium; It is preferable to treat without heavy metal ions.

The organic oxidizing agent suitable for the present invention is preferably, for example, di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, t-butyl hydroperoxide, p-menthol hydroperoxide or mixtures thereof; Particularly preferred are cumene hydroperoxide and t-butyl hydroperoxide. Instead of an organic oxidant, H ₂ O ₂ may be used as an oxidizing agent in the oxidation initiator system.

The reducing agent that can be used in accordance with the present invention is preferably a water-soluble compound having a reducing action, and is preferably a salt of sulfinic acid, a salt of sulfurous acid, sodium dithionite, sodium sulfite, sodium hypasulfite, sodium hydrogen sulfite, It is preferably selected from the group consisting of Rongalit ( ^R ) C (sodium formaldehyde sulfoxylate), monohydroxyacetone and dihydroxyacetone, sugar (e.g., glucose or dextrose). It is theoretically possible to use, for example, iron (II) salts such as iron (II) sulfate, tin (II) salts such as tin chloride (II), titanium (III) It is preferred not to use this type of metal salt.

Particularly preferred reducing agents are dextrose, ascorbic acid (salt) or sodium formaldehyde sulfoxylate (Long Galit C).

The graft polymer B.2 used according to the invention is prepared through persulfate initiation.

Suitable persulfate compounds for the present invention are ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, or mixtures thereof.

Co-precipitated Graft  Polymers B.1 and B.2

The preparation of the graft polymers to be used according to the invention can be carried out using at least one graft polymer B.2 in the form of a latex prepared using at least one persulfate compound as an initiator using at least one redox system as an initiator By mixing it with at least one graft polymer B.1 in the form of a latex prepared, wherein the latexes are uniformly mixed and the resulting graft polymer blend product is treated by known procedures.

Examples of suitable treatment processes include precipitation of the graft polymer dispersion mixture by the action of an aqueous electrolyte solution, such as a salt solution (e.g., magnesium sulfate, calcium chloride, sodium chloride), an acid solution (e.g., sulfuric acid, phosphoric acid, acetic acid) Precipitation by low temperature (freeze-solidification) action, or by directly recovering the co-precipitated product by spray drying from the dispersion mixture (latex).

In the case of precipitating the graft polymer mixture, it is followed by a washing step (preferably washing with water) and a drying step (e.g. drying in a fluid bed dryer or flash dryer).

The pH of component B generally has a value of from 3 to 9, preferably from 4 to 8, particularly preferably from 5 to 7. [ To measure the pH of component B, component B is slurried in water immediately after distillation to form a 10% (wt%) suspension.

The graft polymers B.1 and B.2 can be co-precipitated in any mixing ratio. The weight ratio of B.1: B.2 is preferably 95: 5 to 5:95, particularly preferably 90:10 to 25:75, particularly preferably 85:15 to 50:50.

As another process, the graft polymer mixture wet in the kneader reactor is mixed with the thermoplastic resin melt (component C) after the precipitation step. The details of this process are disclosed in EP-A 867 463. The molding composition according to the present invention can be produced by using the graft polymer mixture obtained by the above process and the composition comprising the thermoplastic resin by the component C. Where the co-precipitated graft polymer B is preferably present in a dispersed form in a matrix of vinyl (co) polymer C.1 (especially styrene / acrylonitrile copolymer). Here, the weight ratio of B: C.1 is preferably 90:10 to 10:90, more preferably 80:20 to 30:70, and particularly preferably 70:30 to 40:60.

Theoretically, the graft polymer component and the vinyl (co) polymer component C.1 and / or polyalkylene terephthalate component obtained by co-precipitation of polycarbonate or polyester carbonate component A, B.1 and B.2 C.2 and optional additives may be mixed together in a conventional compounding device in the compounding step, then mixed with the other ingredients and further processed in a conventional manner. It is also possible to mix components B and C separately from other components and additives and further treat them.

Component C

Component C comprises at least one thermoplastic vinyl (co) polymer C.1 and / or polyalkylene terephthalate C.2.

Suitable as vinyl (co) polymer C.1 are vinyl aromatic, vinyl cyanide (unsaturated nitrile), (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids : Anhydride and imide). Copolymers of the following C.1.1 and C.1.2 are particularly suitable:

C.1.1 vinyl aromatic and / or ring substituted vinyl aromatic such as styrene,? -Methylstyrene, p-methylstyrene, p-chlorostyrene and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters such as methyl 50 to 99 parts by weight, preferably 60 to 80 parts by weight, of methacrylate and ethyl methacrylate, and

C.1.2 Vinyl cyanide (unsaturated nitrile) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t Butyl acrylate, and / or unsaturated carboxylic acids such as derivatives of maleic acid and / or unsaturated carboxylic acids (e.g. anhydrides and imides) such as maleic anhydride and N-phenylmaleimide, preferably 1 to 50 parts by weight, Is 20 to 40 parts by weight.

The vinyl (co) polymer C.1 is a dendritic thermoplastic (co) polymer and is rubber-free. Copolymers of C.1.1 styrene and C.1.2 acrylonitrile are particularly preferred.

The (co) polymers according to C.1 are well known and can be prepared by free radical polymers, in particular emulsions, suspensions, solutions or bulk polymers. The (co) polymer preferably has an average molecular weight M _w (determined by weight average molecular weight, light scattering or sedimentation) of 15,000 to 200,000.

The polyalkylene terephthalate of component C.2 is the reaction product of an aromatic dicarboxylic acid or a reactive derivative thereof, such as a dimethyl ester or anhydride, and an aliphatic, cycloaliphatic or araliphatic diol, and a mixture of such reaction products.

Preferred polyalkylene terephthalates are those having a terephthalic acid group content of at least 80 wt%, preferably at least 90 wt% based on the dicarboxylic acid component, and at least 80 wt%, preferably at least 90 mol% ethylene Glycol and / or 1,4-butanediol group.

The preferred polyalkylene terephthalate may contain, in addition to the terephthalic acid group, up to 20 mol%, preferably up to 10 mol%, of other C ₈ -C ₁₄ aromatic or cycloaliphatic dicarboxylic acids or C ₄ -C ₁₂ aliphatic dicarboxylic acids Such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexane diacetic acid Group.

Preferred polyalkylene terephthalates are those containing not more than 20 mol%, preferably not more than 10 mol% of other C ₃ -C ₁₂ aliphatic diols or C ₆ -C ₂₁ cycloaliphatic diols in addition to the ethylene glycol or 1,4- 1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2, Propane diol, 2,5-hexanediol, 1,4-di- (? -Hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4 -? - hydroxyethoxyphenyl) propane and 2,2- Propoxy) propane (DE-A 2 407 674, 2 407 776, 2 715 932).

The polyalkylene terephthalate can be branched for example by incorporating a relatively small amount of tri- or tetra-alcohol or tribasic or tetra-basic carboxylic acid according to DE-A 1 900 270 and US-PS 3 692 744 have. Examples of preferred branching agents include trimethic acid, trimellitic acid, trimethylol ethane and trimethylol propane, and pentaerythritol.

Particularly preferred are polyalkylene terephthalates prepared with only terephthalic acid and reactive derivatives thereof (e.g., dialkyl esters of terephthalic acid) and ethylene glycol and / or 1,4-butanediol, and mixtures of such polyalkylene terephthalates.

The mixture of polyalkylene terephthalates may contain polyethylene terephthalate in an amount of 1 to 50 wt%, preferably 1 to 30 wt%, and polybutylene terephthalate in an amount of 50 to 99 wt%, preferably 70 to 99 wt% Lt; / RTI >

The polyalkylene terephthalate which is preferably used is generally used in an amount of from 0.4 to 1.5 dl / g, preferably from 0.5 to 1 dl / g, as measured by a Ubbelohde viscometer at 25 DEG C in phenol / o-dichlorobenzene (1: To 1.2 dl / g.

The polyalkylene terephthalate can be prepared by a known method (see, for example, Kunststoff-Handbuch, volume VIII, pp. 695 ff., Carl-Hanser-Verlag, Munich 1973).

Component D

In the present invention, the phosphorus-containing flame retardant (component D) is preferably selected from the group consisting of phosphoric acid and phosphonic acid monoesters and oligomer esters, phosphonate amines and phosphazenes, A mixture of components may also be used as a flame retardant. Other halogen-free compounds which are not specifically mentioned here may be used alone or as a mixture with other halogen-free compounds.

Preferred phosphoric or phosphonic acid monoesters and oligomeric esters are phosphorus compounds represented by formula IV:

(IV)

In this formula,

R ¹ , R ² , R ³ and R ⁴ are each, independently of one another, optionally halogenated C ₁ -C ₈ Alkyl, in each case optionally substituted by alkyl, preferably C ₁ -C ₄ alkyl, and / or by halogen, preferably chlorine or bromine, C ₅ -C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₁₂ aralkyl, alkyl;

n independently from each other represent 0 or 1;

q represents 0 to 30;

X represents a mono- or polynuclear aromatic group having 6 to 30 carbon atoms or a straight-chain or branched-chain aliphatic group having 2 to 30 carbon atoms, which may be OH-substituted and contain 8 or less ether bonds.

It is preferred that R ¹ , R ² , R ³ and R ⁴ independently of _one another denote C ₁ -C ₄ alkyl, phenyl, naphthyl or phenyl-C ₁ -C ₄ alkyl. The aromatic groups R ¹ , R ² , R ³ and R ⁴ may be substituted in this part by halogen and / or alkyl groups, preferably by chlorine, bromine and / or C ₁ -C ₄ alkyl. Particularly preferred aryl groups are cresyl, phenyl, xylanyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives.

In formula (IV), X represents a mononuclear or polynuclear aromatic group having 6 to 30 carbon atoms. This is preferably derived from the diphenols of formula (I).

N in the formula (IV) may be independently 0 or 1; n is preferably equal to 1.

q represents a numerical value of 0 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, even more preferably 0.5 to 6, most preferably 1.1 to 1.6.

X represents in particular the chlorinated or brominated derivatives of the formulas:

;

;

 X is derived in particular from resorcinol, hydroquinone, bisphenol A or diphenyl phenol. It is particularly preferred that X is derived from bisphenol A.

As component D according to the invention, a mixture of different phosphates may also be used.

The phosphorus compound represented by the general formula (IV) specifically includes tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri (isopropylphenyl) Phosphate, resorcinol crosslinked oligophosphate and bisphenol A crosslinked oligophosphate. It is particularly preferred to use phosphoric acid oligomeric esters of formula IV derived from bisphenol A.

Most preferred as component D is a bisphenol A based compound represented by the following formula IVa:

(IVa)

Phosphorus compounds by component D are known or can be prepared in a similar manner by known methods (see, for example, Ullmanns Enzyklopadie der (reference example: EP-A 0 363 608, EP-A 0 640 655) 18, pp. 301, 1979; Houben-Weyl, Methoden der organischen Chemie, vol 12/1, p 43; Beilstein vol. 6, p.

When using various phosphorus compounds, given q is the average q value for compounds that are oligomers. The average q value is calculated by measuring the composition of the phosphorus compound (molecular weight distribution) by a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC) Can be determined by calculation.

In addition, phosphonate amines and phosphazenes as disclosed in WO 00/00541 and WO 01/18105 can be used as flame retardants.

These flame retardants may be used alone or in any mixture, or as a mixture with other flame retardants.

Component E

Suitable phenolic antioxidants are one or more compounds selected from the group consisting of sterically hindered phenols, hydroquinone and hydroquinone analogs, substituted compounds and tocopherol antioxidants, and derivatives thereof.

The sterically hindered phenol may be mononuclear or polynuclear. Also, the sterically hindered phenol may be substituted or crosslinked through a substituent. Sterically hindered phenols include oligomeric compounds that can consist of monomeric compounds and some phenolic parent materials.

Examples of phenolic antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butylcresol (BHT, also known as Ionol 330), tetrakis [methylene- (Di-tert-butyl-4-hydroxycinnamate)] methane (Irganox ^® 1010, 2,2'-methylene-bis (4- Cyanox ^® 2246), benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4-hydroxy-, 1,1 '- (thiodi-2,1-ethanediyl) 1035), 1,1,3-tri (3-tert-butyl-4-hydroxy-6-methylphenyl) butane (Topanol ^® CA), octadecyl 3- (3,5- Butylphenyl) propionate (Irganox 1076), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Santowhite ( ^R ) powder) 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate (Cyanox 1790), 1,3,5- (1H, 3H, 5H) -triene (Goodrite < ( ^R ) > 3114), 1,3,5-tris [2- [3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionyloxy] ethyl] (1H, 3H, 5H) -triene (Goodite 3125), 1,3,5-tris (3,5-di-tert- butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene (Ethanox ^® 330, Irganox 1330), 4,4'-thiobis [2-tert-butyl-5-methylphenol] (Santonox ^® R), 2,2'-methylene bis (6-cyclohexyl-4-methylphenol) (bulka Knox (Vulkanox ^®) ZKF) it is preferred to use at least one compound selected from the group consisting of.

In a particularly preferred embodiment, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is used as component E.

Component F

The neutral phosphorus-containing or sulfur-containing auxiliary stabilizer used in the present invention is specifically a compound which neither contains a basic functional group nor an acidic functional group.

As the neutral-containing and sulfur-containing synergist, tris (nonylphenyl) phosphite (TNPP), tris (2,4-tert- butylphenyl) phosphite (the said force (Irgafos ^®) 168), pentaerythritol bis ( stearyl phosphite) (Weston (Weston ^®) 618), pentaerythritol bis (2,6-di -tert- butylphenol phosphite) (Ultra Knox (Ultranox ^®) 626), tetrakis (2, 4 Butylphenyl) [1,1'-biphenyl] -4,4'-diylbisphosphonite (Sandostab ^® P-EPQ, Irgafos P-EPQ), dialkyl thiodi It is preferable to use at least one compound selected from the group consisting of propionate such as dilauryl thiodipropionate (DLTDP) and distearyl thiodipropionate (DSTDP).

In a particularly preferred embodiment, Irgafos 168 is used as component F.

(I.e., component E) and a synergist (i.e., component F), such as a dialkyl phosphite, a diaryl phosphite (e.g., a diphenyl phosphite Or 2,2'-methylenebis (6-cyclohexyl-4-methylphenyl) phosphite represented by the following formula (VI) is not suitable.

(V)

(VI)

Component G

The composition may comprise as component G other chemical additives, for example, a flame retardant, a rubber modified graft polymer other than component B, a dripping inhibitor such as a fluorinated polyolefin material class of compounds such as polytetrafluoroethylene, Antistatic agents (e.g., conductive carbon black, carbon fibers, carbon nanotubes, and organic antistatic agents such as polyalkylene ethers, alkylsulfone, and the like), lubricants and release agents (e.g., pentaerythritol tetrastearate), nucleating agents, (Such as glass or carbon fibers, mica, kaolin, talc, CaCO ₃ and glass flakes), as well as dyes and pigments.

Graft polymers other than component B are prepared by free radical polymerization, for example by emulsification, suspension, solution or bulk polymer. Graft polymers other than component B prepared by solution or bulk polymer are preferred.

Fluorinated polyolefins are known and are disclosed, for example, in EP-A 0 640 655. These are sold, for example, under the tradename Teflon ^® 30N by DuPont.

The fluorinated polyolefin may also be in the form of a pure, emulsion of the fluorinated polyolefin and an emulsion of the graft polymer by the component B or a (co) polymer based on vinyl monomers, especially styrene / acrylonitrile or methyl methacrylate (Co) polymer, wherein the fluorinated polyolefin coagulates after mixing with the emulsion of the graft polymer or copolymer as an emulsion.

The fluorinated polyolefin may also be used as a pre-compound with a graft polymer component B or a copolymer, preferably a copolymer based on vinyl monomers. The fluorinated polyolefin is mixed with the powder or granules of the graft polymer or copolymer as a powder and is melt-blended in a conventional apparatus such as an internal mixer, an extruder or a twin-screw extruder at a temperature of generally 200 to 330 ° C.

The fluorinated polyolefin may also be used in the form of a masterbatch prepared by emulsion polymerization of one or more monoethylenically unsaturated monomers in the presence of an aqueous dispersion of a fluorinated polyolefin. Preferred monomer components are styrene, acrylonitrile, methyl methacrylate, and mixtures thereof. The polymer is used as a free-flowing powder after acid precipitation and subsequent drying.

The coagulate, free compound or masterbatch generally has a solids content of from 5 to 95% by weight, preferably from 7 to 80% by weight, of the fluorinated polyolefin.

The fluorinated polyolefin is preferably used at a concentration of from 0 to 2% by weight, in particular from 0.1 to 0.5% by weight, based on the sum of parts by weight of component A + B + C, Or data on pure fluorinated polyolefin when masterbatch is used.

Preparation of molding compositions and molded articles

The composition according to the present invention is prepared by melt-extruding the respective components in a known manner, melt-kneading them in a conventional apparatus such as an internal mixer, an extruder and a twin-screw extruder at a temperature of 200 ° C to 300 ° C.

Mixing of the respective components can be carried out continuously in a known manner, and simultaneously, in both cases at about 20 캜 (room temperature) and at a high temperature.

The molding composition according to the present invention can be used to produce any type of molded article. The molded article can be produced by the injection molding, extrusion and blow molding methods. Another treatment method is a method of manufacturing a molded article by thermoforming from a previously prepared sheet or film and an in-mold decoration (IMD) method.

Examples of such molded articles include films, profiles, housing components of any type, such as household appliances such as juice presses, coffee machines, mixers, and the like; For office equipment such as monitors, printers and copiers; Automotive interior and exterior parts; Electrical and electronic components such as panels, pipes, electrical mounting channels, windows, doors and other profiles used in the building and construction sectors (for interior and exterior use) and switches, flocs and sockets.

Specifically, the molding composition according to the present invention can be used, for example, in the production of the following molded articles:

Housings for electrical equipment containing small transformers, housings for information processing and transmission equipment, housings and cladding for medical equipment and massaging equipment, electrical and electronic equipment for railway vehicles, ships, aircraft, buses and other automotive interiors, cladding, and housings used thereon, toy vehicles for children, flat wall elements, housings for security devices, heat-insulated transport containers, equipment used to confine or take care of small animals, molded parts for sanitary and bath articles, Cover grid, sperm and moldings for ourselves and housings for gardening equipment.

Hereinafter, the present invention will be further described with reference to examples.

The present invention also provides a process for producing the composition, a use of the composition for the production of a molded article, and the molded article itself.

Example

Component A

And a weight average molecular weight M _w of 27500 g / mol (measured by GPC at 25 캜 in CH ₂ Cl ₂ ).

Component B

In the following examples, all parts by weight of the graft polymer are obtained by adding together the sum of the weight of the main chain (polybutadiene) and the weight of the graft monomer (styrene and acrylonitrile) in each of the graft polymers given below to 100 parts by weight . The amounts of water, emulsifier, initiator and other adjuvants are based on the sum of the weight parts (= 100 parts by weight) of the main chain and the graft monomer.

Preparation of rubber backbone B2.3:

In the first step, the polybutadiene latexes B2.1 and B2.2 were separately treated with free radical emulsion polymerization of butadiene in the presence of the sodium salt of the TCD emulsifier (see formula VII) disclosed in EP-A 394 779 (Example 1) ≪ / RTI >

(VII)

Preparation of polybutadiene latex B2.1 and B2.2 was carried out by a method known to those skilled in the art that they each have the following specific weight-average particle size d ₅₀ median of:

B2.1: d ₅₀ = 290 nm

B2.2: d ₅₀ = 400 nm

The solids content of the latexes B2.1 and B2.2 is 45% by weight in each case.

In the second step, the polybutadiene latexes B2.1 and B2.2 were mixed together at a weight ratio of 1: 1 (on a solid polymer basis). The resulting polybutadiene rubber main chain B2.3 had a bimodal particle size distribution and a weight average molecular weight of d ₅₀ = 345 nm. The solid content of the polybutadiene rubber main chain B2.3 is 45% by weight.

General Description (I) (Oxidizing Source Initiation):

Type B-I Graft  Preparation of polymer

60 parts by weight of B2.3 (calculated as solid content) was diluted with water so that the solid content was 20% by weight. Subsequently, the mixture was heated to 60 DEG C, 0.3 parts by weight of t-butyl hydroperoxide (dissolved in 20 parts by weight of water) and 0.4 part by weight of sodium ascorbate (dissolved in 20 parts by weight of water) Respectively. Subsequently, the following components were simultaneously supplied within 4 hours, while the reaction temperature was stepwise increased to 80 DEG C within the same 4 hours:

a) 40 parts by weight of a monomer mixture (weight ratio styrene: acrylonitrile = 73: 27), and

b) by using NaOH to adjust the alkalinity (pH = 10-12) the sodium salt of a disproportionated (disproportionated) resin acid dissolved in water (drain if Nate (Dresinate ^®) 731, AVI other Chemie geem beha, germanium STOPEN) 1.5 or 2.2 parts by weight (calculated as solids, the amounts used in each case can be determined from the following components and tables).

The reaction mixture was allowed to stand at 80 DEG C for 2 hours (post-reaction period). Then, 1 part by weight of a phenolic antioxidant was added and mixed.

The resultant graft polymer with a solids content of 32% by weight was then treated (see corresponding general description below).

Overall description ( II ) ( Persulfate  Start):

Type B- II of Graft  Preparation of polymer

60 parts by weight of B2.3 (calculated as solid content) was diluted with water to a solid content of 20% by weight. The mixture was then heated to 60 DEG C and 0.5 parts by weight of potassium peroxodisulfate (dissolved in 25 parts by weight of water) was added.

Subsequently, the following components were simultaneously fed within 6 hours, while the reaction temperature was stepwise increased to 80 ° C within the same 6 hours:

a) 40 parts by weight of a monomer mixture (styrene: acrylonitrile weight ratio 73:27);

b) 0.1 part by weight of t-dodecylmercaptan; And

c) 1.0 or 1.4 g of disodium salt of disproportionated resin acid dissolved in water (pH = 10-12) adjusted to alkaline with NaOH (Dreginate 731, Abieta Chemie GmbH, Gerstopen) (Calculated as solids; the amounts used in each case can be determined from the following ingredients and tables).

The reaction mixture was allowed to stand at 80 DEG C for 2 hours (post-reaction period). Then, 1 part by weight of a phenolic antioxidant was added and mixed.

The resultant graft polymer with a solids content of 32% by weight was then treated (see corresponding general description below).

Overall description (I) or ( II ) Graft  General description of treatment of polymer dispersions:

In the following examples, details of whether the graft polymer dispersions prepared according to general description (I) or (II) are treated separately or as a co-precipitate will be described in detail.

 a) Separate precipitation:

Each of the graft polymer dispersions was added to a precipitating solution (consisting of 2 parts by weight of magnesium sulfate, 1 part by weight of acetic acid and 100 parts by weight of water) at 95 캜 and, after filtration, And dried until it reached less than 0.5% by weight. The pH of the powder slurried in water immediately after distillation to form a 10% (wt.%) Suspension was 6 to 7.

b) co-precipitation:

After mixing 75 parts by weight of the graft polymer dispersion BI (based on the solid content) and 25 parts by weight (based on the solid content) of the graft polymer dispersion B-II, the precipitated solution (2 parts by weight of magnesium sulfate, And 100 parts by weight of water), followed by filtration, and the obtained powder was dried under vacuum at 70 캜 until the residual water content reached less than 0.5% by weight. The pH of the powder slurried in water immediately after distillation to form a 10% (wt.%) Suspension was 6 to 7.

Component B1 (1)

ABS emulsion graft polymer prepared according to general description (I) using 1.5 parts of Dreginate 731 and treated by separate precipitation.

Component B1 (2)

ABS emulsion graft polymer prepared according to general description (I) using 2.2 parts of Dreginate 731 and treated by separate precipitation.

Component B2 (1)

ABS emulsion graft polymer prepared according to general description (II) using 1.0 part of Dreginate 731 and treated by separate precipitation.

Component B2 (2)

ABS emulsion graft polymer prepared according to general description (II) using 1.4 parts of Dreginate 731 and treated by separate precipitation.

Component B (1)

75 parts by weight (based on solids) of graft polymer dispersion B-I prepared according to general description (I) using 1.5 parts of Dreginate 731 and

ABS emulsified graft polymer prepared by co-precipitation of 25 parts by weight (based on solids) of graft polymer dispersion B-II prepared according to general description (II) using 1.0 part of Dreginate 731.

Component B (2)

75 parts by weight (based on solids) of graft polymer dispersion B-I prepared according to general description (I) using 2.2 parts of Dreginate 731 and

ABS emulsion graft polymer prepared by co-precipitation of 25 parts by weight (based on solids) of graft polymer dispersion B-II prepared according to general description (II) using 1.4 parts of Dreginate 731.

Component C

Copolymer of 25% by weight styrene and 75% by weight acrylic (weight-average molecular weight M _w is 130 kg / mol (measured by GPC) and prepared by a bulk polymerization method): C-1

C-2: styrene 72 copolymer of 28% by weight of acrylonitrile,% by weight of acrylic (the weight-average molecular weight M _w is 100 kg / mol (measured by GPC) and prepared by a bulk polymerization method)

Component D

D-1: bisphenol A diphenyl diphosphate (Reofos BAPP, Great Lakes)

D-2: Triphenylphosphate (Disflamoll TP, Lancez)

Component E

E-1: octadecyl - 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (steric hindered phenol, Irganox 1076, Cibasphere alattenkemmi)

E-2: 2,2'-methylenebis (6-cyclohexyl-4-methylphenyl) phosphite (used as an acid phosphite stabilizer)

Component F

F-1: Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168, Cibasphere Alatten Chemical)

F-2: DLTDP (dilauryl thiodipropionate) (ABCR)

Component G

G-1: Pentaerythritol tetrastearate

G-2: Poly (tetrafluoroethylene (PTFE, CFP 6000N, DuPont)

Preparation and testing of molding compositions

Mixing of the components used with conventional processing aids was carried out in a ZSK 25 twin-screw extruder or a 1.3 liter internal mixer. The molded article was produced on an Arburg 270E injection molding machine at 240 캜, 260 캜 or 300 캜.

The composition of the molding composition can be seen from Tables 1 to 4 below.

The evaluation of intrinsic color / natural color was carried out by measuring the yellowness index (YI) of a color sample sheet having dimensions of 60 X 40 X 2 mm with ASTM standard E-313-96 (illuminant: C, observer: 2 °, (128X-106Z) / Y (where X, Y, and Z are the color coordinates according to DIN 5033) based on the surface area (surface area value). The yellowness index was expressed as YI / 260 ° C or YI / 300 ° C, depending on the temperature at which the molded article was produced in an injection molding machine.

As a measure of the hydrolytic resistance of the prepared compositions, granules were prepared at 260 占 폚 (for compositions without flame retardant) or 240 占 폚 (for compositions containing flame retardant), under a 5 kg load for polycarbonate compositions without flame retardant During storage ("FWL storage") at 95 ° C and 100% relative humidity for 7 days ("FWL storage") and for 2 days at 95 ° C and 100% relative humidity for polycarbonate compositions containing flame retardant The change in MVR measured in accordance with ISO 1133 was used. The increment of the MVR value compared to the MVR value before the storage period was calculated as? MVR (hydrolysis), which is defined by the following equation:

Characterization of the flame retardancy was carried out according to UL 94V (on a bar having dimensions of 127 x 12.7 x 1.5 mm).

As can be clearly seen from the above examples, the impact modified polycarbonate molding composition containing the emulsifying graft polymer (ABS) according to the present invention as an impact modifier can be prepared by adding an optionally added synergist such as a neutral organophosphite (F-1) or a thio compound (F-2) and a phenolic antioxidant (E-1). The emulsion graft polymer (ABS) according to the present invention consists of two components, one polymerized by a redox initiation reaction and the other polymerized by an inorganic persulfate initiating reaction, both components together as an emulsion polymer Are mixed in a dispersion step and co-precipitated as a latex mixture.

Specifically, the compositions 1 and 2 according to the present invention exhibit excellent hydrolytic resistance (ΔMVR (hydrolysis) = 105% or 112%) and exhibit very soft natural color (injection temperature at a melting temperature of 260 ° C. and a molding temperature of 80 ° C. YI 19 after molding, or YI 25 after injection molding at a melting temperature of 300 ° C and a molding temperature of 80 ° C. On the other hand, the composition of Comparative Examples 3, 4, 6 and 7 containing one of the respective components as emulsifying ABS (i.e. B1 (1), B1 (2) or B2 (2) (1) and B2 (1), these components being mixed as a powder and not being mixed at the stage of the emulsion polymer dispersion, unlike the present invention) exhibit excellent hydrolytic resistance, Exhibit inferior natural color (YI > 28 in each case even after injection molding at a melting temperature of 260 DEG C and a molding temperature of 80 DEG C).

These results are also reflected in the second test series (Table 2), but here the overall result of the natural color is inferior due to more severe processing conditions and this results in a longer residence time of the composition in the internal mixer than in the extruder . Thus, the results presented in Table 2 above also demonstrate that the compositions of the present invention are distinguished in that they have excellent natural color and high hydrolytic stability.

All compositions containing the acidic phosphite stabilizer E-2 (comparative example) exhibited inferior hydrolytic resistance and markedly poorer natural color compared to the composition according to the invention, whereas the compositions according to the invention showed a neutral phenolic antioxidant E-1, optionally containing neutral organic phosphite F-1 or thio compound F-2 as a synergist (see Tables 3 and 4).

Claims (15)

A) 10 to 99 parts by weight of an aromatic polycarbonate or an aromatic polyester carbonate, or an aromatic polycarbonate and an aromatic polyester carbonate;
B) A graft polymer obtainable by co-precipitation of a mixture of two or more graft polymer dispersions B.1 and B.2, wherein the graft polymer component B.1 comprises at least one redox system 1 to 50 parts by weight of a graft polymer, wherein the graft polymer component B.2 is prepared by using at least one persulfate compound as an initiator;
C) 0 to 40 parts by weight of a vinyl (co) polymer or polyalkylene terephthalate, or a vinyl (co) polymer and a polyalkylene terephthalate;
D) 0 to 50 parts by weight of a phosphorus-containing flame retardant based on the sum of components A + B + C;
E) from 0.005 to 1 part by weight of at least one phenolic antioxidant based on the sum of components A + B + C;
F) from 0.01 to 2 parts by weight of a neutral phosphorus containing or sulfur-containing auxiliary stabilizer (synergist) based on the sum of components A + B + C; And
G) 0 to 50 parts by weight of an additive based on the sum of component A + B + C
(Component E) containing a basic or acidic functional group and a synergist not containing a basic or acidic functional group-containing synergist (component F) containing a basic or acidic functional group-containing synergist (component F) ), And the sum of the components A + B + C is 100 parts by weight. delete 2. A composition according to claim 1 comprising from 0.02 to 0.3 parts by weight of component E and 0.05 to 0.5 parts by weight of component F (in each case based on the sum of parts by weight of component A + B + C). The composition of claim 1, wherein component B is a graft polymer prepared by co-precipitation of a mixture of two graft polymer dispersions B.1 and B.2, wherein B.1 and B.2 are
i) from 15 to 60% by weight of one or more vinyl monomers,
ii) 85 to 40% by weight of one or more main chains having a glass transition temperature of less than 10 <
Of an aqueous polymer dispersion. The composition of claim 1, wherein the pH of component B is from 3 to 9. The composition of claim 1, wherein the backbone of component B has an average particle size (d ₅₀ ) of 0.2 to 0.4 μm. 2. The composition of claim 1 comprising from 2 to 30 parts by weight of a phosphorus containing flame retardant (based on the sum of parts by weight of component A + B + C) as component D. 8. A composition according to claim 7 comprising as component D a compound which is a monomer and oligomer of formula IV:
(IV)

In this formula,
R ¹ , R ² , R ³ and R ⁴ are each independently of one another optionally halogenated C ₁ -C ₈ alkyl, in each case optionally alkyl-substituted or halogen-substituted, or alkyl- and halogen-substituted C ₅ -C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₁₂ aralkyl;
n independently from each other represent 0 or 1;
q represents 0 to 30;
X represents a monocyclic or polycyclic aromatic radical having 6 to 30 carbon atoms or a straight or branched chain aliphatic radical having 2 to 30 carbon atoms which may be OH-substituted and contain up to 8 ether linkages . The composition according to claim 1, wherein component E is
Di-tert-butylphenol, 2,6-di-tert-butylcresol, tetrakis [methylene- (3,5- Methylene-bis (4-methyl-6-tert-butylphenol), benzenepropanoic acid-3,5-bis (1,1-dimethylethyl) -4- 1,1,3-tri (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, octadecyl-3- (3,5- Butylphenyl) propionate, 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (2,6- tert-butyl-3-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert- butyl-4-hydroxybenzyl) (1H, 3H, 5H) -triene, 1,3,5-tris [2- [3- (3,5-di- tert- butyl-4- hydroxyphenyl) propionyloxy] ethyl] Triazine-2,4,6 (1H, 3H, 5H) -thione, 1,3,5-tris (3,5-di-tert- butyl-4-hydroxyphenylmethyl) -Trimethylbenzene, 4,4'-thiobis [2-tert-butyl-5-methylphenol], and 2,2'-methylenebis (6-cyclohexyl-4-methylphenol). The composition according to claim 1, wherein component F is
(2,4-tert-butylphenyl) phosphite, pentaerythritol bis (stearyl phosphite), pentaerythritol bis (2,6-di-tert-butylphenol phosphite ), Tetrakis (2,4-di-tert-butylphenyl) [1,1'-biphenyl] -4,4'-diylbisphosphonite, dilauryl thiodipropionate, Wherein the composition is at least one compound selected from the group consisting of aliphatic polyisocyanates, polyisocyanates, and diisopropionates. A method for producing a molded article using the composition according to claim 1. A molded article comprising the composition according to claim 1. 13. A shaped article according to claim 12, characterized in that it is a part of an automobile, a railway vehicle, an aircraft or a ship, or any type of sheet, profile or housing part. delete delete